The present invention relates to a cyanoacrylate composition having photocurability. Possible applications of the composition include lithography, potting, molding, coating, adhesives, sealing materials, and various resist materials.
xcex1-Cyanoacrylate adhesives are extensively utilized as cold-setting single-liquid type instantaneous adhesives for metals, plastics, rubbers, woods, etc., because they rapidly polymerize and cure by the action of a minute amount of the adsorption water present on adherend surfaces to extremely tenaciously bond the adherends to each other in a short time period.
However, the xcex1-cyanoacrylate adhesives have a drawback that the curing is very slow when the gap between adherends is wide, when the adhesive applied has overflown from the bonding part, or when the adhesive applied is not sandwiched between a pair of adherends as in coating.
In general, a cyanoacrylate adhesive with which a large gap is filled or which has overflown from a bonding part is cured by using a primer or a curing accelerator. However, not only this technique is troublesome, but also the basic compound used as the main component of the primer or curing accelerator and the odor of the solvent contained therein are undesirable for the working environment.
There is hence a desire for a cyanoacrylate adhesive which can be easily cured without impairing the excellent features of the instantaneous adhesive, i.e., cold-setting and single-liquid type.
To eliminate the problem described above, cyanoacrylate adhesive compositions having photocurability have been proposed. For example, a cyanoacrylate adhesive composition containing a radical-generating photopolymerization initiator is disclosed in JP-A-62-57475. (The term xe2x80x9cJP-Axe2x80x9d as used herein means an xe2x80x9cunexamined published Japanese patent application.xe2x80x9d)
JP-A-6-299122 discloses an adhesive composition containing an aromatic azide compound as a photoinitiator for anionic polymerization.
WO93/10483 discloses a technique in which an inorganic chromium complex is used as a photoinitiator for anionic polymerization.
Further, a technique of using Pt(acac)2 as a photoinitiator for anionic polymerization is reported in Macromolecules, 28 (4) 1328 (1995).
These proposed compositions, however, have problems such as the following. In order for the compositions to cure, a relatively long light irradiation time of from 1 to 2 minutes is necessary. In the case of radical polymerization, the curing reaction is inhibited by oxygen and, as a result, the adhesive surface suffers curing failure or remains tacky. Moreover, the compositions foam upon light irradiation, or have poor storage stability.
On the other hand, many proposals have been made on photocurable compositions containing a metallocene compound as a photoinitiator. Metallocene compounds are generally used as a photoinitiator for radical polymerization or cationic polymerization. For example, JP-A-6-35189 discloses a photopolymerizable mixture containing a photoinitiator comprising (A) a photoreducible dye, (B) a radiation-decomposable trihalomethyl compound, and (C) a metallocene compound and a recording material produced from the mixture.
JP-A-5-117311 discloses a photopolymerization initiator comprising a complex obtained by the interaction of (A) a charge-transfer complex comprising a biscyclopentadienyliron derivative and a quinoid compound with (B) at least one salt selected from the group consisting of tetrafluoroboric acid salts, hexafluorophosphoric acid salts, and hexafluoroantimonic acid salts.
JP-A-4-221958 discloses a photopolymerizable mixture containing a metallocene compound as a photoreaction initiator and a recording material produced from the mixture.
JP-A-2-127404 discloses a photopolymerizable mixture containing a photoinitiator comprising (A) a photo-reducible dye, (B) a radiation-decomposable trihalomethyl compound, and (C) a metallocene compound and a recording material produced from the mixture.
JP-A-4-73763 discloses a photocurable electrodeposition coating composition containing a titanocene compound as an initiator.
Further, a technique of photocuring a vinyl monomer by means of ferrocene alone or a combination thereof with carbon tetrachloride is reported in J. Macromol. Sci.-Chem., A28 (5and6), 557 (1991).
However, the techniques shown above are based on a polymerization mechanism in which a radical or cationic polymerization reaction proceeds, and are unrelated to the technique for photopolymerizing and curing an xcex1-cyanoacrylate mainly by anionic polymerization, in particular to the technique of the present invention.
An object of the present invention is to provide a photocurable composition having excellent photocurability to overcome the above-described problems in the prior art.
The present inventors have found that the above object is achieved with the following embodiments:
(1) a photocurable composition comprising:
(A) an xcex1-cyanoacrylate and
(B) a metallocene compound comprising a transition metal of Group VIII of the periodic table and aromatic electron system ligands;
(2) the photocurable composition according to the embodiment (1), further comprising (C) a cleavage-type photoinitiator;
(3) the photocurable composition according to the embodiment (1) or (2), wherein in the metallocene compound (B) comprising a transition metal of Group VIII of the periodic table and aromatic electron system ligands, the aromatic electron system ligands each is a xcfx80-arene, indenyl, or xcex7-cyclopentadienyl;
(4) the photocurable composition according to any one of the embodiments (1) to (3), wherein the metallocene compound (B) comprising a transition metal of Group VIII of the periodic table and aromatic electron system ligands is represented by the following formula (I): 
(wherein M represents a transition metal of Group VIII of the periodic table; R represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a silicon atom-containing, oxygen atom-containing, sulfur atom-containing, or phosphorus atom-containing group having 1 to 20 carbon atoms, provided that the R""s may be the same or different and may be crosslinked to each other; symbol a represents an integer of from 0 to 5; and the groups [Ra-Cp] (Cp represents xcex7-cyclopentadienyl) may be the same or different);
(5) the photocurable composition according to any one of the embodiments (1) to (4), wherein in the metallocene compound (B) comprising a transition metal of Group VIII of the periodic table and aromatic electron system ligands, the transition metal of Group VIII of the periodic table comprises iron, osmium, ruthenium, cobalt, or nickel; and
(6) the photocurable composition according to the embodiment (5), wherein in the metallocene compound (B) comprising a transition metal of Group VIII of the periodic table and aromatic electron system ligands, the transition metal of Group VIII of the periodic table comprises iron, osmium, or ruthenium.
The photocurable composition of the present invention can be rapidly cured by light irradiation even when the gap between a pair of adherends is wide, when the composition applied has overflown from the bonding part, or when the composition applied is not sandwiched between a pair of adherends as in coating. Since the curing reaction proceeds by anionic polymerization, not only the composition does not suffer the surface curing inhibition by oxygen which is observed in radical polymerization, but also even that part of the composition which light cannot reach due to the shape of the substrate cures by the anionic polymerization initiated by light irradiation. Further, since the metallocene compound has a light absorption wavelength region extending beyond 500 nm to the longer-wavelength side, the composition can be cured with a light in a wider wavelength region, i.e., even with ultraviolet and/or visible light.
This invention is explained below in detail.
Although the xcex1-cyanoacrylate (A) contained as an essential component in the composition of the present invention is not particularly limited, it is represented by general formula (II):
H2Cxe2x95x90C(CN)xe2x80x94COORxe2x80x83xe2x80x83(II)
(In the formula, R is an ester residue such as, e.g., an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, or aryl group. Although the ester residue is not particularly limited in the number of its carbon atoms, it generally has from 1 to 8 carbon atoms. The ester residue may be a substituted hydrocarbon group such as an alkoxyalkyl or trialkylsilylalkyl group.)
Examples of the cyanoacrylate include alkyl and cycloalkyl xcex1-cyanoacrylates such as methyl xcex1-cyanoacrylate, ethyl xcex1-cyanoacrylate, propyl xcex1-cyanoacrylate, butyl xcex1-cyanoacrylate, and cyclohexyl xcex1-cyanoacrylate; alkenyl and cycloalkenyl xcex1-cyanoacrylates such as allyl xcex1-cyanoacrylate, methallyl xcex1-cyanoacrylate, and cyclohexenyl xcex1-cyanoacrylate; alkynyl xcex1-cyanoacrylates such as propargyl xcex1-cyanoacrylate; aryl xcex1-cyanoacrylates such as phenyl xcex1-cyanoacrylate and tolyl xcex1-cyanoacrylate; heteroatom-containing xcex1-cyanoacrylates such as methoxyethyl xcex1-cyanoacrylate, ethoxyethyl xcex1-cyanoacrylate, and furfuryl xcex1-cyanoacrylate; and silicon-containing xcex1-cyanoacrylates such as trimethylsilylmethyl xcex1-cyanoacrylate, trimethylsilylethyl xcex1-cyanoacrylate, trimethylsilylpropyl xcex1-cyanoacrylate, and dimethylvinylsilylmethyl xcex1-cyanoacrylate.
The metallocene compound (B) comprising a transition metal of Group VIII of the periodic table and aromatic electron system ligands, which is another essential component of the composition of the present invention, is not particularly limited in its aromatic electron system ligands. Desirable examples of the ligands include xcfx80-arenes, indenyl, and xcex7-cyclopentadienyl. Preferred of these is xcex7-cyclopentadienyl.
Examples of substituents which may be bonded to each ligand include halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, halogenated hydrocarbon groups having 1 to 20 carbon atoms, and silicon atom-containing, oxygen atom-containing, sulfur atom-containing, and phosphorus atom-containing groups having 1 to 20 carbon atoms. Each ligand may have the same or different substituents, and the substituents may be crosslinked to each other.
Preferred examples of the metallocene compound comprising a transition metal of Group VIII of the periodic table and aromatic electron system ligands are represented by the following structural formula (I): 
(In the formula, M represents a transition metal of Group VIII of the periodic table. R represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a silicon atom-containing, oxygen atom-containing, sulfur atom-containing, or phosphorus atom-containing group having 1 to 20 carbon atoms, provided that the R""s may be the same or different and may be crosslinked to each other. Symbol a represents an integer of from 0 to 5.)
In formula (1), the groups [Ra-Cp] (Cp represents xcex7-cyclopentadienyl) may be the same or different.
Specific examples of the metallocene compound comprising a transition metal of Group VIII of the periodic table and aromatic electron system ligands include ferrocene, in which the transition metal is iron, osmocene, in which the transition metal is osmium, ruthenocene in which the transition metal is ruthenium, cobaltocene, in which the transition metal is cobalt, and nickelocene, in which the transition metal is nickel. Among these, ferrocene, osmosene and ruthenocene, and derivatives thereof are preferred.
Examples of ferrocene compounds in which the aromatic electron system ligands are substituted with at least one substituent are shown below and in Examples. In the present invention, metallocene compounds having the structures formed by replacing the iron in these ferrocene compounds with another transition metal of Group VIII of the periodic table, e.g., osmium, ruthenium, cobalt or nickel can also be used. The more substituents the metallocene compounds for use in the present invention have, the better photocurability they tend to have.
(i) Examples of compounds having one or more halogen atom substituents include 4-acetyl-1xe2x80x2-bromo-1,2-diethylferrocene, 1xe2x80x2-bromo-1,2,3-triethylferrocene, 1-acetyl-1xe2x80x2-bromo-2,3-diethylferrocene, 1,1xe2x80x2-dibromo-3-(dibromoboryl)ferrocene, 1,1xe2x80x2-dibromo-3,3xe2x80x2-bis(dibromoboryl)ferrocene, 1-bromo-1xe2x80x2-methylferrocene, 1-bromo-1xe2x80x2-(methoxymethyl)-ferrocene, 1-bromo-1xe2x80x2-(4-methylbenzoyl)ferrocene, 1-iodo-1xe2x80x2-(phenylethyl)ferrocene, 1-iodo-1xe2x80x2-(4-methoxyphenyl)ferrocene, 1-(4-chlorophenyl)-1xe2x80x2-iodoferrocene, 1-iodo-1xe2x80x2-phenylferrocene, 1,3-dichloro-2,4,5xe2x80x2-tris(methylthio)ferrocene, 1,2,4-trichloro-3,5-bis(methylthio)ferrocene, 1,2,3,4-tetrachloro-5-(methylthio)ferrocene, 1-iodo-1xe2x80x2-(3-methoxy-3-oxo-1-propyl)ferrocene, 1,1xe2x80x2-dibromoferrocenium, 2-acetyl-1xe2x80x2-bromo-1,3-diethylferrocene, 1xe2x80x2-bromo-1,2,4-triethylferrocene, 1-acetyl-1xe2x80x2-bromo-2,4-diethylferrocene, 1xe2x80x2-bromo-1,3-diethylferrocene, 1xe2x80x2-bromo-1,2-diethylferrocene, 1-acetyl-1xe2x80x2-bromo-3-ethylferrocene, 1-acetyl-1xe2x80x2-bromo-2-ethylferrocene, 1,1xe2x80x2-dichloroferrocenium, decachloroferrocenium, 1-(3-hydroxy-3-methyl-1-butynyl)-1xe2x80x2-iodoferrocene, 1-chloro-1xe2x80x2-ethynylferrocene, 1-bromo-1xe2x80x2-ethynylferrocene, (acetylcyclopentadienyl)(bromocyclo-pentadienyl)iron, (bromocyclopentadienyl)(iodocyclopenta-dienyl)iron, 1-bromo-1xe2x80x2-phenylferrocene, 1-bromo-1xe2x80x2-(triphenylmethyl)ferrocene, 1-bromo-1xe2x80x2-((1-oxooctadecyl)oxy)ferrocene, 1-iodo-1xe2x80x2-((1-oxooctadecyl)oxy)ferrocene, 1-bromo-1xe2x80x2-cuprioferrocene, 1-bromo-1xe2x80x2-pentylferrocene, 1-bromo-1xe2x80x2-(2-methylpropyl)ferrocene, 1-chloro-1xe2x80x2-(3-oxo-3-phenyl-1-propenyl)ferrocene, 1-bromo-1xe2x80x2-formylferrocene, 1-chloro-1xe2x80x2-formylferrocene, 1-bromo-1xe2x80x2-(3-oxo-3-phenyl-1-propenyl)ferrocene, 1-bromo-1xe2x80x2-(2-methyl-1,3-dioxolan-2-yl)ferrocene, 1-bromo-1xe2x80x2-((4-methylphenyl)methyl)ferrocene, 1-bromo-1xe2x80x2-((3-methylphenyl)methyl)ferrocene, 1-bromo-1xe2x80x2-((2-methylphenyl)-methyl)ferrocene, 1-(diphenylphosphino)-1xe2x80x2-iodoferrocene, 1-((3-formylphenyl)ethynyl)-1xe2x80x2-iodoferrocene, 1-((2-formylphenyl)ethynyl)-1xe2x80x2-iodoferrocene, 1,1xe2x80x2-dichloro-2-(trichlorosilyl)ferrocene, (1xe2x80x2,2-dichloroferrocenyl)lithium, 1-chloro-1xe2x80x2-phenylferrocene, 1-((4-formylphenyl)ethynyl)-1xe2x80x2-iodoferrocene, 1-(capryoethynyl)-1xe2x80x2-iodoferrocene, decabromoferrocene, formylnonaiodoferrocene, ethylnonaiodoferrocene, nonaiodomethylferrocene, nonabromoformylferrocene, acetylnonaiodoferrocene, 1-(ethoxycarbonyl)-1xe2x80x2-iodoferrocene, 1-bromo-1xe2x80x2-(ethoxycarbonyl)ferrocene, 1-chloro-1xe2x80x2-(ethoxycarbonyl)ferrocene, decaiodoferrocene, 1-benzoyl-1xe2x80x2-bromoferrocene, 1-benzoyl-1xe2x80x2-chloroferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2-octachloro-5,5xe2x80x2-diiodoferrocene, 1-iodo-1xe2x80x2-methylferrocene, and decachloroferrocene.
(ii) Examples of compounds having one or more hydrocarbon group substituents having 1 to 20 carbon atoms include 1,1xe2x80x2-dimethylferrocene, 1,1xe2x80x2-di-n-butylferrocene, bis(pentamethylcyclopentadienyl)iron, 1,1xe2x80x2-diethylferrocene, 1,1xe2x80x2-dipropylferrocene, 1,1xe2x80x2-di-n-pentylferrocene, 1,1xe2x80x2-di-n-hexylferrocene, 1,1xe2x80x2,2-trimethylferrocene, 1,1xe2x80x2,2-triethylferrocene, 1,1xe2x80x2,2-tripropylferrocene, 1,1xe2x80x2,2-tri-n-butylferrocene, 1,1xe2x80x2,2-tri-n-pentylferrocene, 1,1xe2x80x2,2-tri-n-hexylferrocene, 1,1xe2x80x2,3-trimethylferrocene, 1,1xe2x80x2,3-triethylferrocene, 1,1xe2x80x2,3-tripropylferrocene, 1,1xe2x80x2,3-tri-n-butylferrocene, 1,1xe2x80x2,3-tri-n-pentylferrocene, 1,1xe2x80x2,3-tri-n-hexylferrocene, 1,1xe2x80x2,2,2xe2x80x2-tetramethylferrocene, 1,1xe2x80x2,2,2xe2x80x2-tetraethylferrocene, 1,1xe2x80x2,2,2xe2x80x2-tetrapropylferrocene, 1,1xe2x80x2,2,2xe2x80x2-tetra-n-butylferrocene, 1,1xe2x80x2,2,2xe2x80x2-tetra-n-pentylferrocene, 1,1xe2x80x2,2,2xe2x80x2-tetra-n-hexylferrocene, 1,1xe2x80x2,2,3xe2x80x2-tetramethylferrocene, 1,1xe2x80x2,2,3xe2x80x2-tetraethylferrocene, 1,1xe2x80x2,2,3xe2x80x2-tetrapropylferrocene, 1,1xe2x80x2,2,3xe2x80x2-tetra-n-butyl-ferrocene, 1,1xe2x80x2,2,3xe2x80x2-tetra-n-pentylferrocene, 1,1xe2x80x2,2,3xe2x80x2-tetra-n-hexylferrocene, 1,1xe2x80x2,3,3xe2x80x2-tetramethylferrocene, 1,1xe2x80x2,3,3xe2x80x2-tetraethylferrocene, 1,1xe2x80x2,3,3xe2x80x2-tetrapropylferrocene, 1,1xe2x80x2,3,3xe2x80x2-tetra-n-butylferrocene, 1,1xe2x80x2,3,3xe2x80x2-tetra-n-pentylferrocene, 1,1xe2x80x2,3,3xe2x80x2-tetra-n-hexylferrocene, 1,1xe2x80x2,2,3-tetramethylferrocene, 1,1xe2x80x2,2,3-tetraethylferrocene, 1,1xe2x80x2,2,3-tetrapropylferrocene, 1,1xe2x80x2,2,3-tetra-n-butylferrocene, 1,1xe2x80x2,2,3-tetra-n-pentylferrocene, 1,1xe2x80x2,2,3-tetra-n-hexylferrocene, 1,1xe2x80x2,2,4-tetramethylferrocene, 1,1xe2x80x2,2,4-tetraethylferrocene, 1,1xe2x80x2,2,4-tetrapropylferrocene, 1,1xe2x80x2,2,4-tetra-n-butylferrocene, 1,1xe2x80x2,2,4-tetra-n-pentylferrocene, 1,1xe2x80x2,2,4-tetra-n-hexylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3-pentamethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3-pentaethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3-pentapropylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3-penta-n-butylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3-penta-n-pentylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3-penta-n-hexylferrocene, 1,1xe2x80x2,2,2xe2x80x2,4-pentamethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,4-pentaethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,4-pentapropylferrocene, 1,1xe2x80x2,2,2xe2x80x2,4-penta-n-butylferrocene, 1,1xe2x80x2,2,2xe2x80x2,4-penta-n-pentylferrocene, 1,1xe2x80x2,2,2xe2x80x2,4-penta-n-hexylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2-pentamethylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2-pentaethylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2-pentapropylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2-penta-n-butylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2-penta-n-pentylferrocene, 1,1xe2x80x2,2,3,3-penta-n-hexylferrocene, 1,1xe2x80x2,2,3xe2x80x2,4-pentamethylferrocene, 1,1xe2x80x2,2,3xe2x80x2,4-pentaethylferrocene, 1,1xe2x80x2,2,3xe2x80x2,4-pentapropylferrocene, 1,1xe2x80x2,2,3xe2x80x2,4-penta-n-butylferrocene, 1,1xe2x80x2,2,3xe2x80x2,4-penta-n-pentylferrocene, 1,1xe2x80x2,2,3xe2x80x2,4-penta-n-hexylferrocene, 1,1xe2x80x2,2,3,4-pentamethylferrocene, 1,1xe2x80x2,2,3,4-pentaethylferrocene, 1,1xe2x80x2,2,3,4-pentapropylferrocene, 1,1xe2x80x2,2,3,4-penta-n-butylferrocene, 1,1xe2x80x2,2,3,4-penta-n-pentylferrocene, 1,1xe2x80x2,2,3,4-penta-n-hexylferrocene, 1,1xe2x80x2,2,3,4,5-hexamethylferrocene, 1,1xe2x80x2,2,3,4,5-hexaethylferrocene, 1,1xe2x80x2,2,3,4,5-hexapropylferrocene, 1,1xe2x80x2,2,3,4,5-hexa-n-butylferrocene, 1,1xe2x80x2,2,3,4,5-hexa-n-pentylferrocene, 1,1xe2x80x2,2,3,4,5-hexa-n-hexylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4-hexamethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4-hexaethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4-hexapropylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4-hexa-n-butylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4-hexa-n-pentylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4-hexa-n-hexylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4-hexamethylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,3,4-hexaethylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4-hexapropylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4-hexa-n-butylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4-hexa-n-pentylferrocene, 1,1xe2x80x2, 2,3,3xe2x80x2,4-hexa-n-hexylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2-hexamethylferrocene, 1 ,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2-hexaethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2-hexapropylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2-hexa-n-butylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2-hexa-n-pentylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2-hexa-n-hexylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3xe2x80x2,4-hexamethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3xe2x80x2,4-hexaethylferrocene, 1,1xe2x80x2,2xe2x80x2,2xe2x80x2,3xe2x80x2,4-hexapropylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3xe2x80x2,4-hexa-n-butylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3xe2x80x2,4-hexa-n-pentylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3xe2x80x2,4-hexa-n-hexylferrocene, 1,1xe2x80x2,2,2xe2x80x2,4,4xe2x80x2-hexamethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,4,14xe2x80x2-hexaethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,4,4xe2x80x2-hexapropylferrocene, 1,1xe2x80x2,2,2xe2x80x2,4,4xe2x80x2-hexa-n-butylferrocene, 1,1xe2x80x2,2,2xe2x80x2,4,4xe2x80x2-hexa-n-pentylferrocene, 1,1xe2x80x2,2,2xe2x80x2,4,4xe2x80x2-hexa-n-hexylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4,5-heptamethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4,5-heptaethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4,5-heptapropylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4,5-hepta-n-butylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4,5-hepta-n-pentylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4,5-hepta-n-hexylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4,5-heptamethylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4,5-heptaethylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4,5-heptapropylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4,5-hepta-n-butylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4,5-hepta-n-pentylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4,5-hepta-n-hexylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4-heptamethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4-heptaethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4-heptapropylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4-hepta-n-butylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4-hepta-n-pentylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4-hepta-n-hexylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4,4xe2x80x2-heptamethylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4,4xe2x80x2-heptaethylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4,4xe2x80x2-heptapropylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4,4xe2x80x2-hepta-n-butylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4,4xe2x80x2-hepta-n-pentylferrocene, 1,1xe2x80x2,2,3,3xe2x80x2,4,4xe2x80x2-hepta-n-hexylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,5-octomethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,5-octoethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,5-octopropylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,5-octo-n-butylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,5-octo-n-pentylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,5-octo-n-hexylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4,4xe2x80x2,5-octomethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4,4xe2x80x2,5-octoethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4,4xe2x80x2,5-octopropylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4,4xe2x80x2,5-octo-n-butylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4,4xe2x80x2,5-octo-n-pentylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,4,4xe2x80x2,5-octo-n-hexylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5-nonamethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5-nonaethylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5-octopropylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5-octo-n-butylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5-octo-n-pentylferrocene, 1,1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5-octo-n-hexylferrocene, bis(pentaethylcyclopentadienyl)iron, bis(pentapropylcyclopentadienyl)iron, bis(penta-n-butylcyclopentadienyl)iron, bis(penta-n-pentylcyclopentadienyl)iron, bis(penta-n-hexylcyclopentadienyl)iron, 1,1xe2x80x2-dimethyl-2-ethylferrocene, 1,1xe2x80x2-dimethyl-3-ethylferrocene, 1,1xe2x80x2-di-n-butyl-3-methylferrocene, 1,1xe2x80x2-di-n-butyl-3-ethylferrocene, 1,1xe2x80x2-dimethyl-3,3xe2x80x2-diethylferrocene, 1,1xe2x80x2,2-trimethyl-3-ethylferrocene, 1,1xe2x80x2-ditriphenylmethylferrocene, 1-methyl-1xe2x80x2-triphenylmethylferrocene, and 1-n-butyl-1xe2x80x2-triphenylmethylferrocene.
(iii) Examples of compounds having one or more halogenated hydrocarbon group substituents having 1 to 20 carbon atoms include 1-methyl-1xe2x80x2-(chloromethyl)ferrocene, 1-chloro-1xe2x80x2-(chloromethyl)ferrocene, 1-methyl-1xe2x80x2-(bromomethyl)ferrocene, 1-methyl-1xe2x80x2-(iodomethyl)ferrocene, 1,1xe2x80x2-di(chloromethyl)ferrocene, 1,1xe2x80x2,2-tri(chloromethyl)ferrocene, l1,1xe2x80x2,2,2xe2x80x2-tetra(chloromethyl)ferrocene, bis(pentachloromethylcyclopentadienyl)iron, bis(pentabromomethylcyclopentadienyl)iron, 1-methyl-1-(trichloromethyl)ferrocene, 1-ethyl-1xe2x80x2-(trichloromethyl)ferrocene, 1-methyl-1xe2x80x2-(tribromomethyl)ferrocene, 1-methyl-1xe2x80x2-(triiodomethyl)ferrocene, 1-chloro-1xe2x80x2-(trichloromethyl)ferrocene, 1-bromo-1xe2x80x2-(trichloromethyl)ferrocene, 1-bromo-1xe2x80x2-(tribromomethyl)ferrocene, 1,1xe2x80x2-di(trichloromethyl)ferrocene, 1,1xe2x80x2-di(tribromomethyl)ferrocene, 1,1xe2x80x2-di(trichloromethyl)-2-chloroferrocene, 1-acetyl-1xe2x80x2-(trichloromethyl)ferrocene, 1,1xe2x80x2-diacetyl-2-(trichloromethyl)ferrocene, 1,1xe2x80x2-diacetyl-3-(trichloromethyl)ferrocene, 1-formyl-1xe2x80x2-(((chloromethyl)oxy)methyl)ferrocene, 1xe2x80x2-acetyl-1-(((chloromethyl)oxy)methyl)ferrocene, 1-formyl-1xe2x80x2-(((trichloromethyl)oxy)methyl)ferrocene, and 1-acetyl-1-(((trichloromethyl)oxy)methyl)ferrocene.
(iv) Examples of compounds having one or more silicon atom-containing group substituents having 1 to 20 carbon atoms include 1-formyl-1xe2x80x2-(((trimethylsilyl)oxy)methyl)ferrocene, 1-(((6-(((1,1-dimethylethyl)dimethylsilyl)oxy)hexyl)oxy)methyl)-1xe2x80x2-formylferrocene, 1-acetyl-1xe2x80x2-(((trimethylsilyl)oxy)methyl)ferrocene, 1-(((6-(((1,1-dimethylethyl)dimethylsilyl)oxy)hexyl)oxy)methyl)-1xe2x80x2-acetylferrocene, 1,1xe2x80x2-di(((trimethylsilyl)oxy)methyl)ferrocene, 1,1xe2x80x2-di(((6-(((1,1-dimethylethyl)dimethylsilyl)oxy)hexyl)oxy)methyl)ferrocene, 1,1xe2x80x2-di(((trimethylsilyl)oxy)methyl)-2-acetylferrocene, 1,1xe2x80x2-di(((6-(((1,1-dimethylethyl)dimethylsilyl)oxy)hexyl)oxy)methyl)-2-acetylferrocene, 1,1xe2x80x2-di(((trimethylsilyl)oxy)methyl)-2-formylferrocene, 1,1xe2x80x2-di(((6-(((1,1-dimethylethyl)dimethylsilyl)oxy)hexyl)oxy)methyl)-2-formylferrocene, 1-methyl-1xe2x80x2-(((trimethylsilyl)oxy)methyl)ferrocene, 1-(((6-(((1,1-dimethylethyl)dimethylsilyl)oxy)hexyl)oxy)methyl)-1xe2x80x2-methylferrocene, 1-ethyl-1xe2x80x2-(((trimethylsilyl)oxy)methyl)ferrocene, 1-(((6-(((1,1-dimethylethyl)dimethylsilyl)oxy)hexyl)oxy)methyl)-1xe2x80x2-ethylferrocene, 1,1xe2x80x2-di(((trimethylsilyl)oxy)methyl)-2-methylferrocene, 1,1xe2x80x2-di(((6-(((1,1-dimethylethyl)-dimethylsilyl)oxy)hexyl)oxy)methyl)-2-methylferrocene, 1-methyl-1xe2x80x2-(trimethylsilylmethyl)ferrocene, 1-methyl-1xe2x80x2-(trimethylsilylethyl)ferrocene, 1-methyl-1xe2x80x2-(trimethylsilylpropyl)ferrocene, 1,1xe2x80x2-di(trimethylsilylmethyl)ferrocene, 1,1xe2x80x2-di(trimethylsilylethyl)ferrocene, 1,1xe2x80x2-di(dimethylsilylmethyl)ferrocene, 1-acetyl-1xe2x80x2-(trimethylsilylmethyl)ferrocene, 1,1xe2x80x2-diacetyl-2-(trimethylsilylmethyl)ferrocene, and 1,1xe2x80x2-diacetyl-3-(trimethylsilylmethyl)ferrocene.
(v) Examples of compounds having one or more oxygen atom-containing group substituents having 1 to 20 carbon atoms include 1,1xe2x80x2-di(acetylcyclopentadienyl)iron, 1,1xe2x80x2-dibenzoylferrocene, 1,1xe2x80x2-bis(1-oxotetradecyl)ferrocene, 1-(3-ethoxy-1-methyl-3-oxo-1-propenyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-benzoyl-1xe2x80x2-(3-ethoxy-1-methyl-3-oxo-1-propenyl)ferrocene, 1-(3-ethoxy-1-methyl-3-oxo-1-propenyl)-1xe2x80x2-(phenylacetyl)ferrocene, 1,1xe2x80x2-bis(2-furanylcarbonyl)ferrocene, 1,1xe2x80x2-bis(3-methylbenzoyl)ferrocene, 1-(1,3-dioxopentyl)-1-methylferrocene, (neopentylcyclopentadienyl)(propionylcyclopentadienyl)iron, (pivaloylcyclopentadienyl)(propylcyclopentadienyl)iron, 1-(9-carboxy-1-oxononyl)-1xe2x80x2,3-dimethylferrocene, 1-(9-carboxy-1-oxononyl)-1xe2x80x2,2-dimethylferrocene, 1-(10-ethoxy-1,10-dioxodecyl)-1xe2x80x2,3-dimethylferrocene, 1-(10-ethoxy-1,10-dioxodecyl)-1xe2x80x2,2-dimethylferrocene, 1-(6-methoxy-1,6-dioxohexyl)-1xe2x80x2-(1-oxooctadecyl)ferrocene, 1,1xe2x80x2-bis(1-oxononyl)ferrocene, 1-(1-methyl-3-oxo-1-butenyl)-1xe2x80x2-(phenylacetyl)ferrocene, 1-(3-carboxy-1-oxopropyl)-1xe2x80x2-(1-oxoundecyl)ferrocene, 1-(3-carboxy-1-oxopropyl)-1xe2x80x2-(1-oxononyl)ferrocene, 1-(4-ethoxy-1,4-dioxobutyl)-1xe2x80x2-(1-oxoundecyl)ferrocene, 1-(4-ethoxy-1,4-dioxobutyl)-1xe2x80x2-(1-oxononyl)ferrocene, 1,1xe2x80x2-bis(6-carboxy-1-oxohexyl)ferrocene, 1-(5-carboxy-1-oxopentenyl)-1xe2x80x2-(3-carboxy-1-oxopropyl)ferrocene, 1,1xe2x80x2-bis(7-methoxy-1,7-dioxoheptyl)ferrocene, 1-(4-methoxy-1,4-dioxobutyl)-1xe2x80x2-(6-methoxy-1,6-dioxohexyl)ferrocene, bis(o-carboxybenzoylcyclopentadienyl)iron, (cinnamoylcyclopentadienyl)(neopentylcyclopentadienyl)iron, 1,1xe2x80x2-bis(3,5,5-trimethyl-1-oxohexyl)ferrocene; 1,1xe2x80x2-bis(1-oxohexadecyl)ferrocene, (neopentylcyclopentadienyl)(3,5,5-trimethylhexanoylcyclopentadienyl)iron, (neopentylcyclopentadienyl)(pivaloylcyclopentadienyl)iron, ((4-carboxybutyryl)cyclopentadienyl)((3-carboxypropynoyl)cyclopentadienyl)iron, 1,1xe2x80x2-bis(4-carboxy-1-oxobutyl)ferrocene, (isobutylcyclopentadienyl)(pivaloylcyclopentadienyl)iron, (isobutyrylcyclopentadienyl)(neopentylcyclopentadienyl)iron, 1-(5-carboxypentyl)-1xe2x80x2-(1-oxooctadecyl)ferrocene, 1-(5-carboxy-1-oxopentyl)-1xe2x80x2-octadecylferrocene, 1-(5-carboxy-1-oxopentyl)-1xe2x80x2-(1-oxooctadecyl)ferrocene, ((3-carboxypropionyl)cyclopentadienyl)((3-carboxypropyl)cyclopentadienyl)iron, (benzylcyclopentadienyl)(pivaloylcyclopentadienyl)iron, 1-(9-carboxy-1-oxononyl)-1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5-octamethylferrocene, 1-(10-ethoxy-1,10-dioxodecyl)-1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5-octamethylferrocene, (neopentylcyclopentadienyl)(phenylacetylcyclopentadienyl)iron, (phenethylcyclopentadienyl)(pivaloylcyclopentadienyl)iron, 1,1xe2x80x2-bis(5-methoxy-1,5-dioxopentyl)ferrocene, 1-benzoyl-1xe2x80x2-(1-oxohexadecyl)ferrocene, 1-acetyl-1xe2x80x2-(1-oxohexadecyl)ferrocene, 1,1xe2x80x2-bis(1-oxooctadecyl)ferrocene, 1-acetyl-1xe2x80x2-(1-cyclohexen-1-ylacetyl)ferrocene, 1-acetyl-1xe2x80x2-(1-cycloocten-1-ylacetyl)ferrocene, 1-formyl-1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5-octamethyl-5xe2x80x2-(2,4,6-trimethylbenzoyl)ferrocene, 1-benzoyl-1xe2x80x2-formyl-2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5,5xe2x80x2-octamethylferrocene, benzoylnonamethylferrocene, 1-(3,3-dimethyl-1-oxobutyl)-1-oxobutyl)-1xe2x80x2-(1-oxo-4-phenylbutyl)ferrocene, 1-(1-oxo-5-(4-(1-oxo-3-phenyl-2-propynyl)phenyl)pentyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propynyl)ferrocene, 1-(1-oxo-4-(4-(1-oxo-3-phenyl-2-propynyl)phenyl)butyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propynyl)ferrocene, 1-(1-oxo-3-phenyl-2-propynyl)phenyl)propyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propynyl)ferrocene, 1-(1-oxo-3-(4-(1-oxo-3-phenyl-2-propenyl)phenyl)propyl)-1xe2x80x2- (1-oxo-3-phenyl-2-propynyl)ferrocene, 1-(1-oxo-3-phenylpropyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propynyl)ferrocene, 1-(phenylacetyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propynyl)ferrocene, 1-(1-oxo-5-phenylpentyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(1-oxo-4-phenylbutyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(1-oxo-3-phenyl-2-propenyl)-2-propenyl)-1xe2x80x2-(1-oxo-3-phenylpropyl)ferrocene, 1-benzoyl-1xe2x80x2-formylferrocene, 1-benzoyl-1xe2x80x2-(3-oxo-3-phenyl-1-propenyl)ferrocene, 1,1xe2x80x2-bis(1-oxo-2-pentenyl)ferrocene, 1-benzoyl-1xe2x80x2-(1-hydroxy-3-(1-hydroxycyclohexyl)-1-phenyl-2-propynyl)ferrocene, 1,1xe2x80x2-bis(3-carboxy-1-oxopropyl)ferrocene, 1,1xe2x80x2-bis(4-methoxy-1,4-dioxobutyl)ferrocene, 1-acetyl-1xe2x80x2-(1,3-dioxobutyl)-3,3xe2x80x2-dimethylferrocene, 1,1xe2x80x2-bis(1-oxopentyl)ferrocene, ((3-carboxypropionyl)ethylcyclopentadienyl)(ethylcyclopentadienyl)iron, 1,1xe2x80x2-bis(4-(2-methylbutyl)benzoyl)ferrocene, 1,1xe2x80x2-bis(1-oxoundecyl)ferrocene, 1-(4-hydroxyphenyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-acetyl-1xe2x80x2-(3-(3-methoxyphenyl)-1-oxo-2-propenyl)ferrocene, 1-acetyl-1xe2x80x2-(3-(4-methylphenyl)-1-oxo-2-propenyl)ferrocene, 1-acetyl-1xe2x80x2-(3-(4-methoxyphenyl)-1-oxo-2-propenyl)ferrocene, 1-(3-methyl-1-oxo-2-butenyl)-1xe2x80x2-(phenylacetyl)ferrocene, 1-(4,4-dimethyl-1-oxo-2-pentenyl)-1xe2x80x2-(phenylacetyl)ferrocene, 1-acetyl-1xe2x80x2-(4,4-dimethyl-1-oxo-2-pentenyl)ferrocene, 1-acetyl-1xe2x80x2-(3-methyl-1-oxo-2-butenyl)ferrocene, 1-acetyl-1xe2x80x2-(1-oxo-2-butenyl)ferrocene, 1-acetyl-1xe2x80x2-(2-methyl-1-oxo-2-propenyl)ferrocene, 1-(3,3-dimethyl-1-oxobutyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(3-methyl-1-oxobutyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(1-oxobutyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1,1xe2x80x2-bis((4-methylphenyl)acetyl)ferrocene, 1,1xe2x80x2-bis(3-(4-methylphenyl)-1-oxo-2-propenyl)ferrocene, 1,1xe2x80x2-bis(3-(2-furanyl)-1-oxo-2-propenyl)ferrocene, 1,1xe2x80x2-bis(hydroxyacetyl)ferrocene, 1-(6-(4-methoxyphenyl)-6-oxohexyl)-1xe2x80x2,3-bis(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(10-(4-methoxyphenyl)-10-oxodecyl)-1xe2x80x2,2-bis(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(5-(4-methoxyphenyl)-5-oxopentyl)-1xe2x80x2,3-bis(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(9-(4-methoxyphenyl)-9-oxononyl)-1xe2x80x2,2-bis(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(8-(4-methoxyphenyl)-8-oxooctyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1,1xe2x80x2-bis(10-ethoxy-1,10-dioxodecyl)ferrocene, 1,1xe2x80x2-bis(9-ethoxy-1,9-dioxononyl)ferrocene, 1,1xe2x80x2-bis(8-ethoxy-1,8-dioxooctyl)ferrocene, 1,1xe2x80x2-bis(7-ethoxy-1,7-dioxoheptyl)ferrocene, 1,1xe2x80x2-bis(5-ethoxy-1,5-dioxopentyl)ferrocene, 1-(1,10-dioxo-10-phenyldecyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(1,9-dioxo-9-phenylnonyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(1,8-dioxo-8-phenyloctyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(1,7-dioxo-7-phenylheptyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-methyl-1xe2x80x2-(4-methylbenzoyl)ferrocene, 1-(2-methoxy-2-oxoethyl)-1xe2x80x2-(4-methylbenzoyl)ferrocene, 1-benzoyl-1xe2x80x2,3-bis(phenylmethyl)ferrocene, 1-benzoyl-1xe2x80x2,2-bis(phenylmethyl)ferrocene, 1-benzoyl-1xe2x80x2-(1-hydroxy-1-phenylethyl)ferrocene, 1,1xe2x80x2-bis(1,1xe2x80x2-biphenyl-4-ylcarbonyl)ferrocene, 1-benzoyl-1xe2x80x2-(1-methylcyclopropyl)ferrocene, 1,1xe2x80x2-bis(3-carboxy-1-oxo-2-propenyl)-2-methylferrocene, 1-methyl-1xe2x80x2,2-bis(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(6-methoxy-1,6-dioxohexyl)-1xe2x80x2-((2-oxocyclopentyl)carbonyl)ferrocene, 1,1xe2x80x2-bis(6-ethoxy-1,6-dioxohexyl)ferrocene, 1-(6-ethoxy-1,6-dioxohexyl)-2-((2-oxocyclopentyl)carbonyl)ferrocene, 1,1xe2x80x2-bis(4-methoxybenzoyl)ferrocene, 1,1xe2x80x2-bis(1-oxooctyl)ferrocene, 1-carboxy-1xe2x80x2-(1,2-dioxopropyl)ferrocene, 1-(methoxycarbonyl)-1xe2x80x2-(phenylacetyl)ferrocene, 1-carboxy-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-carboxy-1xe2x80x2-(oxophenylacetyl)ferrocene, 1-(methoxycarbonyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(3-methylphenyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(4-methylphenyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(1-oxo-3-phenyl-2-propenyl)-1xe2x80x2-phenylferrocene, 1-(3,5-dimethylphenyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(3,4-dimethylphenyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(4-methoxyphenyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(4-(ethoxycarbonyl)phenyl-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-(3-ethylphenyl)-1xe2x80x2-(1-oxo-3-phenyl)-2-propenyl)ferrocene, 1-(4-ethylphenyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1-benzoyl-1xe2x80x2-(methoxymethyl)ferrocene, 1,1xe2x80x2-bis(3-ethoxy-1,3-dioxopropyl)ferrocene, 1-(3,3-dimethyl-1-oxobutyl)-1xe2x80x2,3-dimethylferrocene, 1-(3,3-dimethyl-1-oxobutyl)-1xe2x80x2,2-dimethylferrocene, 1-acetyl-1xe2x80x2-(2-methyl-1-oxo-3-phenyl-2-propenyl)ferrocene, 1-acetyl-1xe2x80x2-(1-oxo-5-phenyl-2,4-pentadienyl)ferrocene, 1,1xe2x80x2-bis(oxophenylacetyl)ferrocene, 1,1xe2x80x2-bis(phenylacetyl)ferrocene, 1-(3-acetylphenyl)-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)ferrocene, 1,1xe2x80x2-bis(cyclohexylcarbonyl)ferrocene, 1,1xe2x80x2-bis(1-oxohexyl)ferrocene, 1,1xe2x80x2-bis(3-methyl-1-oxobutyl)ferrocene, 1-(1,1-dimethylethyl)-1xe2x80x2-(2 ,2-dimethyl-1-oxopropyl)ferrocene, 1-(1,1-dimethylethyl)-1xe2x80x2-(2-methyl-1-oxopropyl)ferrocene, 1-acetyl-1xe2x80x2-(1-oxo-3-phenyl-2-propynyl)ferrocene, 1,1xe2x80x2-bis(2,2-dimethyl-1-oxopropyl)ferrocene,-1-acetyl-1xe2x80x2-(1-oxobutyl)ferrocene, 1-acetyl-1xe2x80x2-(phenylacetyl)-2-(phenylmethyl)ferrocene, 1-benzoyl-1xe2x80x2-(phenylacetyl)ferrocene, 1-(1-oxobutyl)-1xe2x80x2-(phenylacetyl)ferrocene, 1-benzyl-1xe2x80x2-(1-oxobutyl)ferrocene, 1-(1-oxopropyl)-1xe2x80x2-(phenylacetyl)ferrocene, 1-acetyl-1xe2x80x2-(phenylacetyl)ferrocene, 1-benzoyl-1xe2x80x2-(1-oxopropyl)ferrocene, 1-acetyl-3-ethyl-1xe2x80x2-(phenylacetyl)ferrocene, 1-acetyl-1xe2x80x2-(phenylacetyl)-3-(phenylmethyl)ferrocene, 1-(3-ethoxy-1-methyl-3-oxo-1-propenyl)-1xe2x80x2-(1-oxo-2-butenyl)ferrocene, 1-(3-ethoxy-1-methyl-3-oxo-1-propenyl)-1xe2x80x2-(1-oxooctadecyl)ferrocene, 1-(3-ethoxy-1-methyl-3-oxo-1-propenyl)-1xe2x80x2-(1-oxopropyl)ferrocene, 1-acetyl-1xe2x80x2-(3-ethoxy-1-methyl-3-oxo-1-propenyl)ferrocene, 1,1xe2x80x2-bis(((5-((4-methoxyphenoxy)carbonyl)phenoxy)pentyl)oxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((3-(4-((4-methoxyphenoxy)carbonyl)phenoxy)propoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((2-(4-((4-methoxyphenoxy)carbonyl)phenoxy)ethoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((heptadecyloxy)carbonyl)ferrocene, 1,1xe2x80x2-bis(((2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecyn-15-yl)oxy)carbonylferrocene, 1-carboxy-1xe2x80x2-((phenylmethoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((4-((4-hexyloxy)phenoxy)carbonyl)phenoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((4-((4-(pentyloxy)phenoxy)carbonyl)phenoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((4-((4-butoxyphenoxy)carbonyl)phenoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((4-((4-ethoxyphenoxy)carbonyl)phenoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((4-((4-(pentyloxy)benzoyl)oxy)phenoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis(4-((4-(butoxybenzoyl)oxy)phenoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((4-((4-propoxybenzoyl)oxy)phenoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((4-((4-ethoxybenzoyl)oxy)phenoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((4-((4-methoxybenzoyl)oxy)phenoxy)carbonyl)ferrocene, 1-(((1,1xe2x80x2-biphenyl)-4-yloxy)carbonyl)-1xe2x80x2-hexylferrocene, 1-butyl-1xe2x80x2-((4-((4-(pentyloxy)benzoyl)oxy)phenoxy)carbonyl)ferrocene, 1-butyl-1xe2x80x2-((4-hexyloxy)phenoxy)carbonyl)ferrocene, 1-butyl-1xe2x80x2-((4-heptylphenoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((4-formylphenoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis(((3-formylphenyl)methoxy)carbonylferrocene, 1,1xe2x80x2-bis((4-((4-(hexyloxy)benzoyl)oxy)phenoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((4-(phenylmethoxy)phenoxy)carbonylferrocene, 1-((4-(decyloxy)phenoxy)carbonyl)-1xe2x80x2-((4-hydroxyphenoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((4-(decyloxy)phenoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((4-heptyloxy)phenoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((4-(1,1-dimethylethyl)phenoxy)carbonylferrocene, 1,1xe2x80x2-bis(methoxycarbonyl)-2,2xe2x80x2-bis(methoxymethyl)ferrocene, 1,1xe2x80x2-bis(methoxycarbonyl)-2,3xe2x80x2-bis(methoxymethyl)ferrocene, 1,1xe2x80x2-bis(ethoxycarbonyl)-2,3xe2x80x2-bis(methoxymethyl)ferrocene, 1,1xe2x80x2-bis(ethoxycarbonyl)-2,2xe2x80x2-bis(methoxymethyl)ferrocene, 1-(ethoxycarbonyl)-1xe2x80x2,2-bis(methoxymethyl)ferrocene, 1,1xe2x80x2-bis(((1,4-dihydro-1,4-dioxy-2-naphthalenyl)oxy)carbonyl)ferrocene, 1,1xe2x80x2-bis(((4xe2x80x2-(heptyloxy)(1,1xe2x80x2-biphenyl)-4-yl)oxy)carbonyl)ferrocene, 1,1xe2x80x2-bis(((4xe2x80x2-(hexyloxy)(1,1xe2x80x2-biphenyl)-4-yl)oxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((4xe2x80x2-(pentyloxy)(1,1xe2x80x2-biphenyl)-4-yl)oxy)carbonyl)ferrocene, 1,1xe2x80x2-bis(((4xe2x80x2-butoxy(1,1xe2x80x2-biphenyl)-4-yl)oxy)carbonyl)ferrocene, (methoxycarbonyl)nonamethylferrocene, 1,1xe2x80x2-(methoxycarbonyl)-2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5,5xe2x80x2-octamethylferrocene, 1-(2-acetyl-3-oxobutyl)-1xe2x80x2-(methoxycarbonyl)ferrocene, 1-(methoxycarbonyl)-1xe2x80x2-(phenoxymethyl)ferrocene, 1,1xe2x80x2-bis((1,1-dimethylethoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis(((3-hydroxymethyl)phenyl)methoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis(((5-(hydroxymethyl)-2-furanyl)methoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((4-hydroxyphenoxy)carbonyl)ferrocene, 1-acetyl-1xe2x80x2-(propoxycarbonyl)ferrocene, 1-acetyl-1xe2x80x2-(ethoxycarbonyl)ferrocene, decakis(methoxycarbonyl)ferrocene, 1,1xe2x80x2-bis((2-propenyloxy)carbonyl)ferrocene, 1,1xe2x80x2-bis((phenylmethoxy)carbonyl)ferrocene, 1-(ethoxycarbonyl)-1xe2x80x2-ethylferrocene, 1-(ethoxycarbonyl)-1xe2x80x2-methoxyferrocene, 1-(ethoxycarbonyl)-1xe2x80x2-phenylferrocene, 1-acetyl-1xe2x80x2-(4-(ethoxycarbonyl)phenyl)ferrocene, 1,1-bis((oxiranylmethoxy)carbonyl)ferrocene, 1-(hydroxymethyl)-1xe2x80x2-(methoxycarbonyl)ferrocene, 1-(methoxycarbonyl)-1xe2x80x2,2-diphenylferrocene, 1-(methoxycarbonyl)-1xe2x80x2,3-diphenylferrocene, 1,1xe2x80x2-bis(methoxycarbonyl)-3-methylferrocene, 1,2-diformyl-1xe2x80x2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5,5xe2x80x2-octamethylferrocene, 1xe2x80x2-formyl-1,2,3,4-tetramethyl-5-(4,7,10,13-tetraoxatetradec-1-yl)ferrocene, 1-acetyl-1xe2x80x2-(2-ethoxy-2-oxoethyl)ferrocene, 1-formyl-1xe2x80x2-(((6-hydroxyhexyl)oxy)methyl)ferrocene, 1,1xe2x80x2-diacetyl-3,3xe2x80x2-bis(1xe2x80x2-dimethylethyl)ferrocene, 1 xe2x80x2-formyl-1,2,3,4,5-pentamethylferrocene, 1-(1-methyl-3-oxo-1-butenyl)-1xe2x80x2-(1-oxopropyl)ferrocene, 1-acetyl-1xe2x80x2-(1-methyl-3-oxo-1-butenyl)ferrocene, 1xe2x80x2-formyl-1,2-dimethylferrocene, 1-formyl-1xe2x80x2,2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5-octamethylferrocene, (acetylcyclopentadienyl)(neopentylcyclopentadienyl)iron, 1-acetyl-1xe2x80x2-ethynylferrocene, (benzoylcyclopentadienyl)(neopentylcyclopentadienyl)iron, acetylnonamethylferrocene, 1-formyl-1xe2x80x2-(hydroxyphenylmethyl)-2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5,5xe2x80x2-octamethylferrocene, 1-formyl-1xe2x80x2-(1-hydroxyethyl)-2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5,5xe2x80x2-octamethylferrocene, 1-formyl-3-(hydroxymethyl)-1,1xe2x80x2,2,2xe2x80x2,3xe2x80x2,4,4xe2x80x2,5,5xe2x80x2-octamethylferrocene, (acetylcyclopentadienyl)(hydroxycyclopentadienyl)iron, 1xe2x80x2-acetyl-1,2,3,4,5-pentaphenylferrocene, 1,1xe2x80x2-diacetyl-3,3xe2x80x2-dimethylferrocene, (acetylcyclopentadienyl)((2-carboxyvinyl)cyclopentadienyl)iron, (acetylcyclopentadienyl)((2-carboxyethyl)cyclopentadienyl)iron, formylnonamethylferrocene, 1,1xe2x80x2-diformyl-2,2xe2x80x2,3,3xe2x80x2,4,4xe2x80x2,5,5xe2x80x2-octamethylferrocene, 1-formyl-1 -(hydroxymethyl)ferrocene, 1-acetyl-1xe2x80x2-(1-(acetyloxy)ethynyl)ferrocene, 1-acetyl-1xe2x80x2-(8-(4-methoxyphenyl)-8-oxooctyl)ferrocene, 1-acetyl-1xe2x80x2,3-bis(phenylmethyl)ferrocene, 1-acetyl-1xe2x80x2,2-bis(phenylmethyl)ferrocene, 1-acetyl-1xe2x80x2-(1-hydroxy-1-phenylethyl)ferrocene, 1,1xe2x80x2-diacetyl-2-methylferrocene, 1,1xe2x80x2-diacetyl-3-methylferrocene, 1-formyl-2-(4-methoxyphenyl)ferrocene, 1-(3-ethylphenyl)-1xe2x80x2-formylferrocene, 1-(4-ethylphenyl)-1xe2x80x2-formylferrocene, 1-(3,5-dimethylphenyl )-1xe2x80x2-formylferrocene, 1-(4-(ethoxycarbonyl)phenyl)-1xe2x80x2-formylferrocene, 1-(3,4-dimethylphenyl)-1xe2x80x2-formylferrocene, 1-formyl-1xe2x80x2-(4-methoxyphenyl)ferrocene, 1-formyl-1xe2x80x2-(4-methylphenyl)ferrocene, 1-formyl-1xe2x80x2-(3-methylphenyl)ferrocene, 1-acetyl-1xe2x80x2-(4-(acetyloxy)phenyl)ferrocene, 1-formyl-1xe2x80x2-phenylferrocene, 1-acetyl-1xe2x80x2-(4-methoxyphenyl)ferrocene, 1-acetyl-1xe2x80x2-(3,4-dimethylphenyl)ferrocene, 1-acetyl-1xe2x80x2-(3,5-dimethylphenyl)ferrocene, 1-acetyl-1xe2x80x2-(4-methylphenyl)ferrocene, 1-acetyl-1xe2x80x2-phenylferrocene, 1-acetyl-1xe2x80x2-(3-methylphenyl)ferrocene, 1-acetyl-1xe2x80x2-(2-benzoyl-3-oxo-1-butenyl)ferrocene, 1-acetyl-1xe2x80x2-(3-oxo-5-phenyl-1,4-pentadienyl)ferrocene, 1-acetyl-1xe2x80x2-(2-acetyl-5-oxo-5-phenyl-1,3-pentadienyl)ferrocene, 1-acetyl-1xe2x80x2-(5-oxo-5-phenyl-1,3-pentadienyl)ferrocene, 1-acetyl-1xe2x80x2-(1-hydroxyethyl)ferrocene, 1-acetyl-1xe2x80x2-(1-methoxy-3-phenyl-2-propenyl)ferrocene, 1-acetyl-1xe2x80x2,3-bis(1-methylethyl)ferrocene, 1xe2x80x2-acetyl-1,2-dimethylferrocene, 1xe2x80x2-acetyl-1,3-dimethylferrocene, 1-acetyl-1xe2x80x2,3-bis(1,1-dimethylethyl)ferrocene, 1-acetyl-1xe2x80x2-(3-methoxy-3-phenyl-1-propenyl)ferrocene, 1-acetyl-1xe2x80x2,2-bis(1,1-dimethylethyl)ferrocene, 1-acetyl-1xe2x80x2,2-bis(1-methylethyl)ferrocene, 1-acetyl-1xe2x80x2,2-diethylferrocene, 1-acetyl-1xe2x80x2-(3-oxobutyl)ferrocene, 1-acetyl-l,-(3-acetylphenyl)ferrocene, 1-acetyl-1xe2x80x2-(4-acetylphenyl)ferrocene, 1-acetyl-1xe2x80x2-methoxyferrocene, 1-acetyl-1xe2x80x2-(tributylstannyl)ferrocene, and 1-formyl-1xe2x80x2-(tributylstannyl)ferrocene.
(vi) Examples of compounds having one or more sulfur-containing group substituents having 1 to 20 carbon atoms include 1-butyl-1xe2x80x2-(4-mercapto-1-oxobutyl)ferrocenium, 1,1xe2x80x2-bis(4-mercapto-1-oxobutyl)ferrocene, 1-(4-mercapto-1-oxobutyl)-1xe2x80x2-(1-oxobutyl)ferrocene, 1-butyl-1xe2x80x2-(4-mercapto-1-oxobutyl)ferrocene, 1-(2-phenylethyl)-1xe2x80x2-(2-thienylcarbonyl)ferrocene, 1-ethyl-3-(1-hydroxyethyl)-1xe2x80x2-(2-thienylcarbonyl)ferrocene, 1-(phenylacetyl)-1xe2x80x2-(2-thienylcarbonyl)ferrocene, 1-benzoyl-1xe2x80x2-(2-thienylcarbonyl)ferrocene, 1-(1-oxopropyl)-1xe2x80x2-(2-thienylcarbonyl)ferrocene, 1,1xe2x80x2-bis((2-((2-((1,3-dithiol-2-ylidene)-1,3-dithiol-4-yl)thio)ethoxy)carbonyl)ferrocene, 1-(methoxycarbonyl)-1xe2x80x2-((phenylthio)methyl)ferrocene, 1,1xe2x80x2-bis((2-(3-thienyl)ethoxy)carbonyl)ferrocene, 1,1xe2x80x2-bis(((5-(hydroxymethyl)-2-thienyl)methoxy)carbonyl)ferrocene, 1-(methoxycarbonyl)-1xe2x80x2-(methoxysulfonyl)ferrocene, 1-acetyl-1xe2x80x2-(5-acetyl-3-phenyl-2-thienyl)ferrocene, cyclopentadiehyl((1-formyl-2-(2-thienyl)vinyl)cyclopentadienyl)iron, 1-formyl-1xe2x80x2-sulfoferrocene, 1-acetyl-1xe2x80x2-(methoxysulfonyl)ferrocene, and 1-acetyl-1xe2x80x2-sulfoferrocene.
(vii) Examples of compounds having one or more phosphorus-containing group substituents having 1 to 20 carbon atoms include 1,1xe2x80x2-bis(diphenylphosphino)ferrocene, 1-acetyl-1xe2x80x2-((diphenylphosphino)acetyl)ferrocene, 1,1xe2x80x2-bis((diphenylphosphino)acetyl)ferrocene, 1-(diphenylphosphino)-1xe2x80x2-formylferrocene, 1-acetyl-1xe2x80x2-(diphenylphosphino)ferrocene, and 1-acetyl-1xe2x80x2-(diphenylphosphinyl)ferrocene.
(viii) Examples of compounds having substituents crosslinked to each other include 1,1xe2x80x2-diacetyl-2,3xe2x80x2-(1,3-propanediyl)ferrocene, 1,2-diacetyl-1,4xe2x80x2-(1,4-butanediyl)ferrocene, 1,1xe2x80x2-bis(methoxycarbonyl)-2,2xe2x80x2-(oxybis(methylene))ferrocene, 1,1xe2x80x2-bis(ethoxycarbonyl)-2,2xe2x80x2-(oxybis(methylene))ferrocene, 1-benzoyl-1xe2x80x2-(3-oxo-3-phenyl-1-propenyl)-3,3xe2x80x2-(1,3-propanediyl)ferrocene, 1-(phenylacetyl)-1xe2x80x2,3-(1,3-propanediyl)ferrocene, 1-((4-methoxyphenyl)acetyl)-1xe2x80x2,3-(15-pentanediyl)ferrocenei 1-((4-methoxyphenyl)acetyl)-1xe2x80x2,3-(1,3-propanediyl)ferrocene, 1t1xe2x80x2-(1,5-pentanediyl)-3-(phenylacetyl)ferrocene, 1-formyl-1xe2x80x2,3-(1,5-pentanediyl)ferrocene, 1,1xe2x80x2-diacetyl-3,3xe2x80x2-(1,5-pentanediyl)ferrocene, 1-benzoyl-1,2-(1,3-cyclopentanediyl)ferrocene, 1xe2x80x2,2-(1,4-butanediyl)-1-formyl-21,3-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-diacetyl-2xe2x80x2,3-(1,5-pentanediyl)ferrocene, 1-(1-oxo-2-propenyl)-1xe2x80x2,3-(1,3-propanediyl)ferrocene, 1-(methoxycarbonyl)-1xe2x80x2,2-(1,3-propanediyl)ferrocene, 1-acetyl-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)-2xe2x80x2,3-(1,3-propanediyl)ferrocene, 1-acetyl-1xe2x80x2,3-(3-phenyl-1,5-pentanediyl)ferrocene, 1,1xe2x80x2-diacetyl-2,3xe2x80x2-(1,4-butanediyl)ferrocene, 1,1xe2x80x2-diacetyl-3,3xe2x80x2-(1,4-butanediyl)ferrocene, 1,1xe2x80x2-diacetyl-2,3xe2x80x2-(1,4-butanediyl)ferrocene, 1-(methoxycarbonyl)-1xe2x80x2,3-(1,3-propanediyl)ferrocene, 1-formyl-1xe2x80x2,3-(1,3-propanediyl)ferrocene, 1-formyl-1xe2x80x2,2-(1,3-propanediyl)ferrocene, 1xe2x80x2-acetyl-1-(1-oxo-2-propenyl)-2,3xe2x80x2-(1,5-pentanediyl)ferrocene, 1-acetyl-1xe2x80x2-(1-oxo-2-propenyl)-3,3-(1,5-pentanediyl)ferrocene, 1-benzoyl-1xe2x80x2-(3-oxo-3-phenyl-1-propenyl)-3,3xe2x80x2-(1,5-pentanediyl)ferrocene, 1-benzoyl-1xe2x80x2-formyl-3,3xe2x80x2-(1,5-pentanediyl)ferrocene, 1-benzoyl-1xe2x80x2-formyl-3,3xe2x80x2-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-bis(methoxycarbonyl)-2,2xe2x80x2,3,3xe2x80x2-bis(1,3-propanediyl)ferrocene, 1,1xe2x80x2-bis(methoxycarbonyl)-2,2xe2x80x2:4,4-bis(1,3-propanediyl)ferrocene, 1,1xe2x80x2-bis(methoxycarbonyl)-2,4xe2x80x2:2xe2x80x2,4-bis(1,3-propanediyl)ferrocene, 1-(methoxycarbonyl)-1xe2x80x2,2:3xe2x80x2,4-bis(1,3-propanediyl)ferrocene, 1,4-bis(methoxycarbonyl)-1xe2x80x2,2:2xe2x80x2,3-bis(1,3-propanediyl)ferrocene, 1-(methoxycarbonyl)-1xe2x80x2,2:2xe2x80x2,3-bis(1,3-propanediyl)ferrocene, 1xe2x80x2,2-(1,4-butanediyl)-1-(4-methoxy-1,4-dioxobutyl)-2xe2x80x2,3-(1-oxo-1,3-propanediyl)ferrocene, 1,1xe2x80x2-bis(methoxycarbonyl)-2,3xe2x80x2-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-bis(methoxycarbonyl)-3,3 -(1,3-propanediyl)ferrocene, 1-(methoxycarbonyl)-1xe2x80x2,3-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-bis(methoxycarbonyl)-2,2xe2x80x2-(1,3-propanediyl)ferrocene, 1-formyl-1xe2x80x2,2-(1,5-pentanediyl)ferrocene, 1-acetyl-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)-3,3xe2x80x2-(1,5-pentanediyl)ferrocene, 1,1xe2x80x2-bis(1-oxo-3-phenyl-2-propenyl)-3,3xe2x80x2-(1,5-pentanediyl)ferrocene, 1-formyl-1xe2x80x2,2:3xe2x80x2,4-bis(pentanediyl)ferrocene, 1-acetyl-1xe2x80x2,2-(1,3-cyclopentanediyl)ferrocene, 1,1xe2x80x2-diacetyl-3,3xe2x80x2-(1,5-pentanediyl)ferrocene, 1,2-diacetyl-1xe2x80x2,4-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-diacetyl-3,3xe2x80x2-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-diacetyl-2,2xe2x80x2-(1,3-propanediyl)ferrocene, 1,4-diacetyl-1xe2x80x2,2-(1,3-propanediyl)ferrocene, 1-(1-oxo-3-phenyl-2-propenyl)-1,2xe2x80x2-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-bis(1-oxo-3-phenyl-2-propenyl)-3,3xe2x80x2-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-bis(1-oxo-3-phenyl-2-propenyl)-2,3xe2x80x2-(1,3-propanediyl)ferrocene, 1-(1-oxo-3-phenyl-2-propenyl)-1xe2x80x2,3-(1,3-propanediyl)ferrocene, 1-acetyl-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)-3,3xe2x80x2-(1,3-propanediyl)ferrocene, 1-acetyl-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)-2,2xe2x80x2-(1,3-propanediyl)ferrocene, 1-acetyl-1xe2x80x2-(1-oxo-3-phenyl-2-propenyl)-2,3xe2x80x2-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-diacetyl-3,3xe2x80x2-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-diacetyl-2,2xe2x80x2-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-diacetyl-2,3xe2x80x2-(1,3-propanediyl)ferrocene, 1-acetyl-1xe2x80x2,2-(1,3-propanediyl)ferrocene, 1-benzoyl-1xe2x80x2,3-(1,3-propanediyl)ferrocene, 1-benzoyl-1xe2x80x2,2-(1,3-propanediyl)ferrocene, 1-(1-oxopropyl)-1xe2x80x2,3-(1,3-propanediyl)ferrocene, 1-(1-oxopropyl)-1xe2x80x2,2-(1,3-propanediyl)ferrocene, 1-acetyl-1xe2x80x2,3-(1,3-propanediyl)ferrocene, 1-acetyl-1xe2x80x2,3-(4-oxo-1,4-butanediyl)ferrocene, 1-acetyl-1xe2x80x2,2-(4-oxo-1,4-butanediyl)ferrocene, 1-acetyl-1xe2x80x2,2-(1-oxo-1,4-butanediyl)ferrocene, 1-acetyl-1xe2x80x2,3-(5-oxo-1,5-pentanediyl) ferrocene, 1-acetyl-1xe2x80x2,2-(5-oxo-1,5-pentanediyl)ferrocene, 1-acetyl-1xe2x80x2,3-(3-oxo-1,3-propanediyl)ferrocene, 1-acetyl-1xe2x80x2,3-(1-oxo-1,3-propanediyl)ferrocene, 1-acetyl-1xe2x80x2,2-(3-oxo-1,3-propanediyl)ferrocene, 1-acetyl-1xe2x80x2,2-(1-oxo-1,3-propanediyl)ferrocene, 1-acetyl-1xe2x80x2,2:3xe2x80x2,4-bis(1,3-propanediyl)ferrocene, 1-acetyl-1xe2x80x2,3-(1,5-pentanediyl)ferrocene, 1-acetyl-1xe2x80x2,2-(1,5-pentanediyl)ferrocene, 1-acetyl-1xe2x80x2,3-(1,4-butanediyl)ferrocene, 1-acetyl-1xe2x80x2,2-(1,4-butanediyl)ferrocene, 1-formyl-1xe2x80x2,3-(1,3-propanediyl)ferrocene, 1-formyl-1xe2x80x2,2-(1,3-propanediyl)ferrocene, 1-(4-methoxy-1,4-dioxobutyl)-1xe2x80x2,2-(1,3-propanediyl)ferrocene, 1-(4-methoxy-1,4-dioxobutyl)-1xe2x80x2,3- (1,3-propanediyl)ferrocene, 1-(3-carboxy-1-oxopropyl)-1xe2x80x2,2-(1,3-propanediyl)ferrocene, 1-(3-carboxy-1-oxopropyl)-1xe2x80x2,3-(1,3-propanediyl)ferrocene, 1-iodo-1xe2x80x2,2:3xe2x80x2,4-bis(1,3-propanediyl)ferrocene, 1-iodo-1xe2x80x2,3-(1,5-pentanediyl)ferrocene, 1,1xe2x80x2-dibromo-2,2xe2x80x2:3,3xe2x80x2:5,5xe2x80x2-tris(1,3-propanediyl)ferrocene, 1,1xe2x80x2-dichloro-2,2xe2x80x2-(diphenylsilylene)ferrocene, 1,1xe2x80x2-dichloro-2,2xe2x80x2-(dichlorosilylene)ferrocene, 1,1xe2x80x2-diiodo-2,3xe2x80x2-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-dibromo-2,3xe2x80x2-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-diiodo-3,3xe2x80x2-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-dibromo-3,3xe2x80x2-(1,3-propanediyl)ferrocene, 1-iodo-1xe2x80x2,3-(1,3-propanediyl)ferrocene, 1-bromo-1xe2x80x2,3-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-diiodo-2,2xe2x80x2-(1,3-propanediyl)ferrocene, 1,1xe2x80x2-dibromo-2,2xe2x80x2-(1,3-propanediyl)ferrocene, 1-iodo-1 ,2-(1,3-propanediyl)ferrocene, 1-bromo-1xe2x80x2,2-(1,3-propanediyl)ferrocene, 1-chloro-1xe2x80x2,3-(1,5-dioxo-3-phenyl-1,5-pentanediyl)ferrocene, 1-bromo-1 ,3-(1,5-dioxo-3-phenyl-1,5-pentanediyl)ferrocene, and 1-bromo-1xe2x80x2,3-(3-carboxy-1,5-dioxo-1,5-pentanediyl)ferrocene.
The cleavage-type photoinitiator (accelerator) (C) for use in the present invention is not particularly limited. Examples of the cleavage-type photoinitiator are given in Examples and below. Namely, examples thereof include (i) acetophenone photoinitiators such as 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 4-t-butyltrichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1; (ii) benzoin photoinitiators such as benzoin, benzoin methyl ethers benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin methyl ketal; and (iii) other photoinitiators including xcex1-acyloxime esters, acylphosphine oxides, methylphenyl glyoxylate, 3,3xe2x80x2,4,4xe2x80x2-tetra(t-butylperoxycarbonyl)benzophenone, and 2,2xe2x80x2-azobis(2-methylbutyronitrile).
In the case where the cleavage-type photoinitiator used is a peroxide, heating can also be used to cure the composition. In the case where the cleavage-type photoinitiator used is an azo compound, the composition can be foamed by regulating the addition amount of the photoinitiator or the quantity of light with which the composition is irradiated.
The photocurable composition of the present invention is prepared by mixing and stirring the xcex1-cyanoacrylate (A), the metallocene compound (B) comprising a transition metal of Group VIII of the periodic table and aromatic electron system ligands, and the cleavage-type photoinitiator (C) to completely dissolve the components (B) and (C) in the component (A). In the case where heating and stirring are required to dissolve the component (C), heating and stirring are conducted at a temperature such that the component (A) is not degraded in quality or decomposed (generally up to about 60xc2x0 C.). The component (B) is dissolved in a similar manner as in the component (C). In general, the component (B) can be dissolved in the component (A) so that it is necessary to heat and stir the component (B).
During and after adding the component (B) and (C), especially the component (C), to the component (A), the reaction system must be maintained to be shaded.
The component (C) is added to the component (B) in limited amounts while stirring, so as not to add all the component (C) at a time.
The above components each may be a single compound or a mixture of two or more compounds.
The addition amount of the component (B), which varies widely depending on kinds of the component (B), is 10 to 100,000 ppm by weight, preferably 30 to 50,000 ppm by weight, more preferably 50 to 10,000 ppm based on the weight of the component (A).
The addition amount of the component (C), which varies widely depending on kinds and addition amount of the component (B) and kinds of the component (C), is 100 to 20,000 ppm by weight, preferably 300 to 15,000 ppm by weight, more preferably 500 to 10,000 ppm based on the weight of the component (A).
The addition amount of the component (B) can be reduced by adding the component (C) to the component (A).
In the case where the respective components are a mixture comprising two or more ingredients, the total amount of the ingredients of each component is the above addition amount.
The composition may further contain one or more of the following ingredients as long as the effect of the present invention is not impaired.
(1) anionic-polymerization inhibitors
(2) radical-polymerization inhibitors
(3) thickening agents
(4) specific additives such as curing accelerators, plasticizers, tougheners, and heat stabilizers
(5) perfumes, dyes, pigments, etc.
A radical-polymerizable compound such as an acrylic ester, can be added to the photocurable composition of the present invention. Even if a radical-polymerizable compound is added, the photocurable composition of the present invention can be rapidly cured owing to the cleavage-type photoinitiator.
An anionic-polymerization inhibitor may be added in order to enhance the storage stability of the composition. Known examples thereof include sulfur dioxide, sulfur trioxide, nitrogen oxide, hydrogen fluoride, and p-toluenesulfonic acid. The anionic-polymerization inhibitor may be added in an amount of 0.1 to 10,000 ppm by weight based on the weight of the component (A).
Examples of radical-polymerization inhibitors include quinone, hydroquinone, t-butylcatechol, and p-methoxyphenol. The radical-polymerization inhibitor may be added in an amount of 0.1 to 10,000 ppm by weight based on the weight of the component (A).
A thickening agents may be added in order to heighten the viscosity of the composition. Examples thereof include polymethacrylates (including poly(methyl methacrylate)), methacrylate copolymers, acrylic rubbers, cellulose derivatives, poly(vinyl acetate), and poly(xcex1-cyanoacrylate)s.
Many kinds of polymeric additives may be added usually for toughening. Examples thereof include acrylic elastomers, acrylonitrile copolymer elastomers, fluoroelastomers, and a fine silica filler. These substances function also as thickening agents. Other additives known to artisans may be used in the present invention.
The curing of the photocurable composition of the present invention includes two kinds of curing, i.e., curing by anionic polymerization caused by a minute amount of the adsorption water present on adherend surface and curing by anionic photopolymerization caused by light irradiation using a metallocene compound.
The method for curing the photocurable composition of the present invention using light irradiation comprises coating an adherends with the photocurable composition and irradiating the composition with electron beam, ultraviolet light, visible light or near infrared light using a high pressure mercury lamp, a halogen lamp, a xenon lamp or sunlight. Effective wavelength of the irradiated light varies with kinds of the metallocene compound and cleavage-type photoinitiator. Ultraviolet light and visible light are preferred.
The photocurable composition of the present invention may be applied to various known uses as well as, in particular, to sealing of electronic parts, to furnishing a reel seat or fishing-line guides on a fishing rod, to fixing wires such as a coil, to filling for use in dental remedy, and to bonding or decorating an artificial nail.